MXPA99011695A - Filled polymer compositions - Google Patents

Abstract

A filled polymer composition which comprises (A) from 5 to 90 percent of one or more thermoplastic substantially random interpolymers prepared by polymerizing one or more&agr;-olefin monomers with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, and optionally with other polymerizable ethylenically unsaturated monomer(s), and (B) from 10 to 95 percent of one or more inorganic fillers, the amounts of (A) and (B) being based on the total weight of (A) and (B). Fabricated articles made from the filled polymer compositions are useful as sound insulating or energy absorbing films or sheets or as floor, wall or ceiling coverings.

Description

POLYMERIC COMPOSITIONS WITH LOADS This invention relates to charged inter-polymeric α-olefin / vinylidene monomer compositions, and articles made therefrom. Fillers are frequently used to improve the rigidity of polymer compositions, or to decrease the coefficient of linear thermal expansion, or to decrease the overall cost of the polymer composition. However, such charges are well known to simultaneously decrease the impact behavior or strength of the resulting composition. For example, Joseph A. Randosta & Nikhil C. Trivedi in Talco. { published in the Manual of Loads and Reinforcers for Plastics 160 (Harry S. Katz &John V. Milewski eds.)} confirm that the impact performance of polymeric materials is generally diminished by the presence of rigid loads, especially below the glass transition temperature (Tg) of the matrix material, due to the action of the loads as "stress concentrators" . Typically, the filler is incorporated at levels that range from 1 to 50 weight percent of the formulation, depending on the density of the filler. At relatively high levels of charge amount (eg, greater than about 20%), typical thermoplastic formulations (eg, polypropylene, an elastomeric rubber and talcum) have very poor impact performance and do not work well in applications such as boards. automotive Impact resistance at low temperature generally becomes more critical when the formulation is exposed to temperatures approaching the glass transition temperature of the rubber used in the formulation. Sometimes, resistance to room temperature can still be increased in highly charged formulations, but impact resistance at low temperature decreases rapidly with decreasing temperature. Patent application WO 95/09945 describes a thermosetting elastomeric composition comprising a substantially random inter-layered interpolymer of (a) 15 to 70 weight percent of an α-olefin, (b) 30 to 70 weight percent of an aromatic vinylidene compound and (c) 0 to 15 weight percent of a diene. The substantially randomly attached interpolymer is typically mixed with a filler, an oil, and a curing agent at an elevated temperature to make the compound. The amount of the curing agent is typically 0.5 to 12 weight percent, based on the total weight of the formulation. Black smoke can be added in an amount of up to 50 weight percent, based on the total weight of the formulation, to mask the color, to increase the strength and / or decrease the cost of the formulation. The described thermosetting formulations are useful in hoses, air ducts, brake cups, roofing materials and in various automotive parts, such as rims and moldings. However, the post-extrusion curing results in a thermoplastic inter-laced part that can not be reprocessed as a thermoplastic. This limits the recyclability of the product. U.S. Patent No. 5,576,374 discloses thermoplastic olefin compositions having good impact performance at low temperature and modulus of elasticity. They comprise: (A) a thermoplastic resin selected from thermoplastic polyurethanes, polyvinyl chlorides, styrenics, engineering thermoplastics, and polyolefins. (B) At least one substantially linear ethylene / α-olefin polymer which is characterized as having: a) a molten flow rate, I10 I2, > 5.63, b) a molecular weight distribution, Mw / Mn, defined by the equation: Mw / Mn < (I? 0/12) -4.63, and c) a critical cutting regime at the beginning of the melt surface fracture of at least 50 percent greater than the critical cutting regime at the beginning of the melt surface fracture of a polymer linear ethylene / α-olefinic having approximately the same I2 and Mw / Mn, and C) at least one charge.

The charged thermoplastic olefin compositions are said to be useful as automotive fenders, decks, wheel decks and grills and freezer containers. In view of the wide ranges of desirable properties and uses for the thermoplastic polymers, it would be desirable to provide novel polymer compositions with fillers. In one aspect, the present invention relates to a charged polymer composition comprising: (A) from 5 to 90 percent of one or more substantially random thermoplastic interpolymers prepared by the polymerization of one or more α-olefin monomers with one or more vinylidene aromatic monomers and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally with other ethylenically unsaturated polymerizable monomer (s), and (B) from 10 to 95 percent of a more inorganic fillers, the amounts of (A) and (B) being based on the total weight of (A) and (B). In another aspect, the present invention relates to a manufactured article made from such a charged polymer composition. In still another aspect, the present invention relates to a multilayer structure wherein at least one layer is made from such a charged polymer composition.

Surprisingly it has been found that substantially randomly made thermoplastic interpolymers that have been prepared by polymerizing one or more α-olefinic monomers with one or more aromatic vinylidene monomers and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally with other ethylenically unsaturated polymerizable monomer (s) can be mixed with high levels of one or more inorganic fillers and that manufactured articles made from charged polymeric compositions comprising one or more such Thermoplastic interpolymers and one or more inorganic fillers in the aforementioned weight ratios have a substantially improved hardness and tensile modulus while generally maintaining good elongation properties, such as stress at breaking, breaking stress and breaking energy, compared with manufactured items made from an inte corresponding thermoplastic polymer without the inclusion of a charge. It has also been found that, surprisingly, fabricated articles made from charged polymeric compositions comprising one or more such thermoplastic interpolymers and one or more inorganic fillers in the aforementioned weight ratios often have a better scratch resistance than the compositions charged thermoplastic olefins described in the US Patent , Do not. ,576,374. The term "interpolymer" is used herein to mean a polymer wherein at least two different monomers are polymerized to make the interpolymer. The term "substantially random" in the substantially random interpolymer resulting from the polymerization of one or more α-olefinic monomers and one or more aromatic vinylidene monomers or clogged aliphatic or cycloaliphatic vinylidene monomers, and optionally, with another (s) ethylenically unsaturated polymerizable monomer (s) as used herein preferably means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second statistical model of Markovian, as described in DETERMINATION OF SEQUENCE POLYMERIC, Carbon NMR Method 13. from J.C. Randall, Academic Press New York, 1977, pp. 71 -78. Preferably, the substantially random interpolymer resulting from the polymerization of one or more α-olefinic monomers and one or more aromatic vinylidene monomers, and optionally, with other ethylenically unsaturated polymerizable monomer (s) it contains no more than 15 percent of the total amount of aromatic vinylidene monomer in aromatic vinylidene monomer blocks of more than three units. More preferably, the interpolymer was not characterized by a high degree of isotacticity or syndiotacticity. This means that in the NMR spectrum of the carbon-1 1 of the interpolymer substantially randomized the peak areas corresponding to the methylene and methine carbons of the main chain representing meso diad sequences or racemic diad sequences should not exceed 75 percent of the total area of peaks of the methylene and methine carbons of the main chain. The aforementioned polymers or polymers suitable in the polymer composition of the present invention are thermoplastic, this means that they can be molded or otherwise formed and reprocessed at temperatures above their melting or softening point. They are not interleaved to a substantial degree, which means that the charged polymeric compositions of the present invention contain no more than 0.4 percent, preferably no more than 0.2 percent, more preferably no more than 0.05 percent of an agent inter-lacer, based on the weight of the interpolymer (s). More preferably, the charged polymeric compositions of the present invention do not contain any measurable amount of an interlacing agent. The interpolymers employed in the present invention include, but are not limited to, substantially random interpolymers prepared by the polymerization of one or more α-olefinic monomers with one or more aromatic vinylidene monomers and / or one or more aliphatic vinylidene monomers or clogged cycloaliphatics, and optionally with other ethylenically unsaturated polymerizable monomer (s). Suitable α-olefin monomers include, for example, α-olefin monomers containing from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. Such preferred monomers include ethylene, propylene, buten-1,4-methyl-1-pentene, hexen-1 and octén-1. More preferred are ethylene or a combination of ethylene with C3-6 oleolefins. These α-olefins do not contain a nucleus or aromatic portion. Suitable aromatic vinylidene monomers that can be used to prepare the interpolymers employed in the charged polymeric compositions of the present invention include, for example, those represented by the following formula I: Ar / (CH2) n R1-C = C (R2) 2 (Formula I) n wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from halo, C? -4 alkyl, and C? _4 haloalkyl; and n has a value from zero to 4, preferably from zero to 2, more preferably zero. Such parlarly suitable monomers include styrene and its minor derivatives substituted with alkyl or halogen. Exemplary monovinylidene aromamonomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene or chlorostyrene, including all isomers of these compounds. Preferred monomers include styrene, α-methyl styrene, minor styrene derivatives substituted with alkyl- (C?-C4) or with phenyl ring, such as, for example, ortho-, meta-, and para-methylstyrene, styrenes with ring halogenated, para-vinyl toluene or mixtures thereof. A most preferred aromamonovinylidene monomer is styrene. By the term "clogged aliphaor cycloaliphavinylidene monomers", it is meant addition-polymerizable vinylidene monomers corresponding to the formula: A] Where A1 is an aliphatic or cycloaliphatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system. By the term "sterically bulky" is meant that the monomer which supports this substituent is normally incapable of addition polymerization by means of normal Ziegler-Natta polymerization catalysts at a comparable rate with ethylene polymerizations. A-olefin monomers containing from 2 to 20 carbon atoms and having a linear aliphatic structure such as propylene, butene-1, hexene-1 and octene-1 are not considered as clogged aliphatic monomers. Preferred aliphatic or cycloaliphatic vinylidene compounds in which one of the carbon atoms supporting ethylenic unsaturation is substituted tertiary or quaternary. Examples of such substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or their derivatives substituted with alkyl or aryl ring, tert-butyl or norbornyl. The most preferred aliphatic or cycloaliphatic blocked vinylidene compounds are the various isomeric vinyl ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2 norbornene. Especially suitable are 1 -, 3-, and 4-vinylcyclohexene. The interpolymers of one or more α-olefins and one or more monovinylidene aromatic monomers and / or one or more aliphatic or clogged cycloaliphatic vinylidene monomers used in the present invention are substantially random polymers. These interpolymers usually contain from 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50, more preferably from 20 to 50 mole percent of at least one aromatic vinylidene monomer and / or aliphatic or cycloaliphatic vinylidene monomer clogged and from 35 to 99.5, preferably 45 to 99, more preferably from 50 to 98, more preferably from 50 to 80 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. Other ethylenically-optionally unsaturated polymerizable monomer (s) (s) include twisted ring olefins such as norbornene and C-alkyl? _? 0 and norbornenes substituted with C6.o aryl, with an interpolymer example being ethylene / styrene / norbornene. The number average molecular weight (Mn) of the interpolymers is usually greater than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000. The melt index I2 according to Method A of ASTM D 1238, condition E, is generally from 0.01 to 50 g / l 0 min., Preferably from 0.01 to 20 g / 10 min., More preferably from 0.1 to 10 g. / 10 min., And more preferably 0.5 to 5 g / min. The glass transition temperature (Tg) of the interpolymers is preferably from -40 ° C to + 35 ° C, preferably from 0 ° C to + 30 ° C, more preferably from + 10 ° C to + 25 ° C, as measured according to the differential mechanical explorer (EMD). Polymerizations and removal of unreacted monomer at temperatures above the autopolymerization temperature of the respective monomers may result in the formation of some amounts of homopolymer polymerization products resulting from the polymerization of free radicals. For example, while preparing the substantially random interpolymer, an amount of atactic vinylidene aromatic homopolymer may be formed due to the homopolymerization of the aromatic vinylidene monomer at elevated temperatures. The presence of aromatic vinylidene homopolymer in general is not detrimental to the purposes of the present invention and can be tolerated. The aromatic vinylidene homopolymer can be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation of a solution with a non-solvent for either the interpolymer or for the aromatic vinylidene homopolymer. For the purpose of the present invention it is preferred that no more than 20 weight percent, preferably less than 15 weight percent based on the total weight of the interpolymers, of aromatic vinylidene homopolymer is present. Polymers made substantially randomly can be modified by grafting, hydrogenation, typical functionalization or other reactions well known to those skilled in the art. The polymers can be easily sulfonated or chlorinated to provide derivatives functionalized according to established techniques. Polymers made substantially randomly can be prepared as described in US Application No. 07 / 545,403 filed July 3, 1990 (corresponding to EP-A-0,416,815) by James C. Stevens et al., And in US Application No. 08 / 469,828 filed June 6, 1995, issued as US Patent No. 5,703, 187. Preferred operating conditions for such polymerization reactions are pressures from atmospheric to 3,000 atmospheres and temperatures from -30 ° C to 200 ° C. Examples of suitable catalysts and methods for preparing interpolymers made substantially randomly are described in U.S. Application No. 07 / 545,403, filed July 3, 1990 (corresponding to EP-A-416,815).; Application of E.U.A., Serial No. 547,718 filed July 3, 1990 (corresponding to EP-A-468,651); Application of E.U.A., No. 07 / 702,475 filed May 20, 1991 (corresponding to EP-A-514,828); Application of E.U.A., No. 07 / 876,268 filed on May 1, 1992 (corresponding to EP-A-520,732); Application of E.U.A., No. 884,966 filed May 15, 1992 (corresponding to WO 93/23412); U.S. Patent No. 5,374,696 filed January 21, 1993; Application of E.U.A., Serial No. 34,434 filed March 19, 1993 (corresponding to WO 94/01647); Application of E.U.A ,. No. 08/241, 523 filed May 12, 1994 (corresponding to WO 94/06834 and EP 0,705,269); as well as U.S. Patents, 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5, 132,380; 5, 188, 192; 5,321, 106; 5,347,024; 5,350,723; 5,374,696; 5,399,635; 5,460,993 and 5,556,928. A-olefin / vinylidene aromatic interpolymers made substantially randomly can also be prepared by the methods described by John G. Bradfute et al., (W.R. Grace &Co.) in WO 95/32095; by R.B. Pannell (Exxon Chemical Patents, Inc.) in WO 94 00500; and in Plastics Technology, p. 25 (September 1992). Substantially random interpolymers comprising at least one α-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrado are also suitable. These interpolymers contain additional signals with intensities greater than three times the peak-to-peak noise. These signals appear in the range of change from 43.75 to 44.25 ppm and 38.0 to 38.5 ppm. Specifically, peaks greater than 44. 1, 43.9 and 38.2 ppm are observed. An NMR proton test experiment indicates that the signals in the chemical change region 43.75 to 44.25 ppm are methino carbons and the signals in the 38.0 to 38.5 ppm region are methylene carbons. In order to determine the carbon-NMR chemical changes of the described interpolymers, the following procedures and conditions are employed. A polymer solution of five to ten percent by weight in a mixture consisting of 50 volume percent of 1,1,1,2-tetrachloroethane-d 2 and 50 volume percent chromium tris (acetylacetonate) is prepared. 0.10 molar in 1,2,4-trichlorobenzene. The NMR spectra are obtained at 130 ° C using a reverse threshold phase shifter, a 90 degree pulse width and a pulse delay of five seconds or more. The spectra are referenced to the methylene signal isolated from the polymer assigned at 30,000 ppm. It is believed that these new signals are due to sequences involving two end-to-end aromatic vinyl monomers preceded and followed by at least one α-olefin insert, for example, a tetradyl ether / styrene / styrene / ethylene wherein the styrene monomer insertions of said tetrads occur exclusively in a 1, 2 (end-to-end) manner. It is understood by one skilled in the art that for such tetrads involving a vinyl aromatic monomer other than styrene and an α-olefin other than ethylene, that tetrad ethylene / vinyl aromatic monomer / vinyl aromatic monomer / ethylene will give NMR peak elevations of carbon - similar but with slightly different chemical changes. These interpolymers are prepared by conducting the polymerization at temperatures from -30 ° C to 250 ° C in the presence of such catalysts as represented by the formula wherein each Cp is independently, each occurrence, a cyclopentadienyl group p-linked to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, more preferably Zr; each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon; each R 'is independently, each occurrence, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon, or two R' groups together may be a 1, 3-butadiene substituted with hydrocarbyl Ci.io; m is 1 or 2; and, optionally, but preferably in the presence of an activating co-catalyst, such as tris (pentafluorophenyl) borate or methylalumoxane (MAO). Particularly suitable cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon, or two R groups together form a divalent derivative of such a group Preferably, R independently of each occurrence is (including all isomers where appropriate) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are joined together forming a ring-fused system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofhrenyl or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic zirconium dichloride- (dimethylsilanediyl (2-methyl-4-phenylindenyl), racemic- (dimethylsilanediyl (2-methyl-4-phenylindenyl)) zirconium 1,4-diphenyl-l , 3-butadiene, racemic- (dimethylsilanediyl (2-methyl-4-phenylindenyl)) zirconium di-C l -4 alkyl, racemic- (dimethylsilanediyl (2-methyl-4-phenylindenyl)) zirconium di-C 1 -4 alkoxide or any combination thereof Additional preparation methods for the interpolymer component (A) of the present invention have been described in the literature Longo and Grassi (Makromol, Chem., Volume 191, pp. 2387 to 2396 [1990] ) and D'Anniello et al (Journal of Applied Polymer Science, Volume 58, pp. 1701 to 1706 [1995]) reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl3) to prepare an ethylene-styrene copolymer Xu and Lin (Polymer Preprints, Am. Chem. Soc, Div. Polym. Chem., Volume 35, pa 686, 687 [1994]) have reported copolymerization using an MgCl2 / TiCl4 / NdCl3 / Al (iBu) 3 catalyst to give random copolymers of styrene and propylene. Lu et al. (Journal of Applied Polymer Science, Volume 53, pp. 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl 4 / NdCl 3 / MgCl 2 / Al (Et) 3 catalyst. Sernetz and Mulhaupt, (Macromol, Chem. Phys., Volume 197, pages 1071 to 1083 [1997]) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Ziegler-Natta Me2Si (Me4Cp) catalysts ( N-tert-butyl) TiCl2 / methylaluminoxane. The manufacture of interpolymers of aromatic α-olefin / vinyl monomers such as propylene / styrene and butadiene / styrene is described in US Patent No. 5,244,996. The charged polymeric composition of the present invention comprises: (A) from 5 to 90 percent of one or more of the interpolymers described above, and (B) from 10 to 95 percent of one or more of the inorganic fillers, with the quantities of (A) and (B) being based on the total weight of (A) and (B). The preferred amounts of inorganic filler depends on the desired end use of the charged polymeric compositions of the present invention. For example, when floor, wall or ceiling tiles are produced, the amount of inorganic filler (s) (B) is preferably 50 to 95 percent, more preferably 70 to 90 percent, based on the total weight of (A) and (B). On the other hand, when sheets for floor, wall or roof are produced, the amount of the inorganic filler (s) (B) is preferably 10 to 70 percent, more preferably 15 to 50 percent , based on the total weight of (A) and (B). For various applications, loading contents of 40 to 90 percent, more preferably 55 to 85 percent, are preferred, based on the total weight of (A) and (B). The preferred inorganic fillers are ionic inorganic materials. Preferred examples of inorganic fillers are talc, calcium carbonate, alumina trihydrate, glass fibers, marble powder, cement powder, clay, feldspar, silica or glass, calcined silica, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, glass microspheres or chalk. Of these charges, barium sulfate, talc, calcium carbonate, silica / glass, glass fibers, alumina, alumina trihydrate and titanium dioxide and mixtures thereof are preferred. The most preferred inorganic fillers are talc, calcium carbonate, barium sulfate, glass fibers and mixtures thereof. It has surprisingly been found that the aromatic interpolymers of α-olefin / vinylidene show high compatibility with inorganic fillers. The composition of the present invention may contain a coupling agent, such as polyethylene grafted with maleic anhydride or polypropylene grafted with maleic anhydride or a known coupling agent of silane / silicone. However, the presence of a coupling agent is not required, even if the load content is 55 weight percent or more. Even in the absence of a coupling agent, articles manufactured with the present invention still exhibit good load holding and good solid state properties. This is unexpected since many of the above-mentioned aromatic a-olefin / vinylidene interpolymers are largely functionalized. The charged polymeric compositions of the present invention may optionally contain up to 50 weight percent, preferably up to 30 weight percent, more preferably up to 20 weight percent, more preferably up to 10 weight percent, of one or more additional components , such as those described below. However, the total amount of the aromatic interpolymer (s) of α-olefin / vinylidene and the filler (s) (B) is generally at least 50 percent, preferably at least less 70 percent, more preferably at least 80 percent and more preferably at least 09 percent, based on the total weight of the charged polymer composition of the present invention. Further preferred optional polymers are monovinylidene aromatic polymers or styrenic block copolymers. Additional, optional, most preferred polymers are homopolymers or interpolymers of aliphatic α-olefins having from 2 to 20 carbon atoms or α-olefins having from 2 to 20 carbon atoms and containing polar groups. Suitable monovinylidene aromatic polymers include homopolymers or interpolymers of one or more vinylidene aromatic monomers, or interpolymers of one or more monovinylidene aromatic monomers and one or more monomers interpolymerizable with themselves other than an aliphatic α-olefin. Suitable monovinylidene aromatic monomers are represented by the following formula: Ar R? -OCH; wherein R 'and Ar have the meanings stated in the preceding Formula I, particularly styrene. Examples of suitable interpolymerizable co-monomers other than a monovinylidene aromatic monomer include, for example, conjugated dienes of C-C6, especially butadiene or isoprene; ethylenically saturated nitriles such as acrylonitrile, methacrylonitrile or ethacrylonitrile, ethylenically unsaturated anhydrides such as maleic anhydride; ethylenically unsaturated amides such as acrylamide, or methacrylamide; ethylenically unsaturated carboxylic acids (both mono- and difunctional) such as acrylic acid and methacrylic acid; esters (especially minor, for example, alkyl esters of C? -C6) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate, or methacrylate, 2-ethylhexyl acrylate, etc.; ethylenically unsaturated dicarboxylic acid imides such as N-alkyl or N-aryl maleimides such as N-phenyl maleimide. Preferred monomers include maleic anhydride, methyl methacrylate, N-phenyl maleimide and acrylonitrile. In some cases it is also desirable to co-polymerize an inter-lane monomer such as a divinyl benzene within the aromatic monovinylidene polymer.

Polymers of monovinylidene aromatic monomers with other interpolymerizable co-monomers contain, polymerized therein, at least 50 weight percent and, preferably, at least 90 weight percent of one or more monovinylidene aromatic monomers. The styrene block polymers are also useful as an additional polymer, optionally in the charged polymer composition of the present invention. The term "block co-polymer" is used herein to mean elastomers having at least one block segment of a hard polymer unit and at least one block segment of a rubber monomer unit. However, the term is not intended to include thermoelastic ethylene interpolymers which are, in general, random polymers. Preferred block copolymers contain hard segments of styrenic-type polymers in combination with segments of saturated or unsaturated rubber monomers. The structure of the block copolymers useful in the present invention is not critical and may be of the linear or radial type, either diblock or triblock, or any combination thereof. Suitable unsaturated block co-polymers include those represented by the following formulas: ABR (-BA) not Ax- (BA-) and-BA wherein each A is a block of polymer comprising a monovinylidene aromatic monomer, preferably styrene, and each B is a block of polymer comprising a conjugated diene, preferably isoprene or butadiene, and optionally an aromatic vinylidene monomer, preferably styrene; R is the remnant of a multifunctional coupling agent; n is an integer from 1 to 5; x is zero or 1; and "y" is a number from zero to 4. Methods for the preparation of such block co-polymers are known in the art. Suitable catalysts for the preparation of useful block copolymers with unsaturated rubber monomer units include lithium-based catalysts and especially lithium-alkyls. U.S. Patent No. 3,595,942 discloses methods suitable for hydrogenation of block copolymers with unsaturated rubber monomer units to form block copolymers with saturated rubber monomer units. The structure of the polymers is determined by their polymerization methods. For example, linear polymers result from the sequential introduction of the desired rubber monomer into the reaction vessel when initiators such as lithium alkyls or dilithiostylebene are used, or by coupling a two-segment block co-polymer with a difunctional coupling agent. Branched structures, on the other hand, can be obtained by the use of suitable coupling agents having a functionality with respect to the block copolymers with unsaturated rubber monomer units of three or more. The coupling can be effected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinyl benzene as well as with certain polar compounds such as silicon halides., siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any coupler residue in the polymer can be ignored by a suitable description of the block copolymers that form a part of the composition of this invention. Suitable block polymers having unsaturated rubber monomer units include, but are not limited to, styrene-butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SIS), α-methylstyrene-butadiene- α-methylstyrene and α-methylstyrene-isoprene-α-methylstyrene. The styrenic portion of the block co-polymer is preferably a styrene polymer or interpolymer and its analogs and homologs including α-methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes. The preferred styrenics are styrene and α-methylstyrene, and particularly preferred is styrene. Block copolymers with unsaturated rubber monomer units can encompass butadiene or isoprene homopolymers or can encompass co-polymers of one or both of these two dienes with a minor amount of styrenic monomer.

Preferred block copolymers with unsaturated rubber monomer units comprise at least one segment of a styrenic unit and at least one segment of an ethylene-butene or ethylene-propylene co-polymer. Preferred examples of such block co-polymers with unsaturated rubber monomer units include styrene / ethylene-butene co-polymers, styrene / ethylene-propylene co-polymers, styrene / ethylene-butene / styrene co-polymers (SEBS), copolymers styrene / ethylene-propylene / styrene (SEPS). The hydrogenation of the block copolymers with unsaturated rubber monomer units is preferably carried out using a catalyst comprising the reaction products of an alkyl aluminum compound with nickel or cobalt carboxylates or alkoxides under such conditions to substantially completely hydrogenate at least 80 percent of the double aliphatic bonds while not more than 25 percent of the double styrenic aromatic bonds are hydrogenated. Preferred block copolymers are those in which at least 99 percent of the aliphatic double bonds are hydrogenated while less than 5 percent of the aromatic double bonds are hydrogenated. The proportion of the styrenic blocks is generally between 8 and 65 weight percent of the total weight of the block co-polymer. Preferably, the block copolymers contain from 10 to 35 weight percent of styrenic block segments and from 90 to 65 weight percent of rubber monomer block segments, based on the total weight of the block copolymer. . The average molecular weights of the individual blocks may vary within certain limits. In most cases, the styrenic block segments will have numbers of average molecular weights in the range of 5,000 to 125,000, preferably from 7,000 to 60,000 while the rubber monomer block segments will have average molecular weights in the range of 10,000 to 300,000, preferably 30,000 to 150,000. The total average molecular weight of the block copolymer is typically in the range of 25,000 to 250,000, preferably 35,000 to 200,000. In addition, the various block copolymers suitable for use in the present invention can be modified by grafting incorporation of minor amounts of functional groups, such as, for example, maleic anhydride by any of the methods well known in the art. Block co-polymers useful in the present invention are commercially available, such as, for example, those supplied by Shell Chemical Company under the designation KRATON ™ and those supplied by Dexco Polymers under the designation VECTOR ™. Preferred additional, optional polymers are homopolymers or interpolymers of aliphatic α-olefins having from 2 to 20, preferably from 2 to 18, more preferably from 2 to 12 carbon atoms or α-olefins having from 2 to 20, preferably from 2 to 18, more preferably 2 to 12 carbon atoms and containing polar groups. Suitable aliphatic α-olefin monomers that introduce polar groups into the polymer include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile and ethacrylonitrile; ethylenically unsaturated anhydrides such as maleic anhydride; ethylenically unsaturated amides such as acrylamide or methacrylamide; ethylenically unsaturated carboxylic acids (both mono- and difunctional) such as acrylic acid and methacrylic acid; esters (especially minor, for example, alkyl esters of C and -Cg) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate or methacrylate, 2-ethylhexyl acrylate; imides of ethylenically unsaturated dicarboxylic acids such as N-alkyl or Naryl maleimides such as N-phenyl maleimide. Preferably, such monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile. Halogen groups that can be included in the polymers from aliphatic α-olefin monomers include fluoride, chloride and bromide; preferably such polymers are chlorinated polyethylenes (CPEs) or polyvinylchloride. Preferred olefinic polymers for use in the present invention are homopolymers or interpolymers of an aliphatic α-olefin, including cycloaliphatic, having from 2 to 18 carbon atoms. Suitable examples are ethylene or propylene homopolymers, and interpolymers of two or more α-olefin monomers. Other preferred olefinic polymers are interpolymers of ethylene and one or more other α-olefins having from 3 to 8 carbon atoms. Preferred co-monomers include 1-butene, 4-methyl-1-pentene, 1 -hexene and 1-ketene. The olefinic polymer may also contain, in addition to the α-olefin, one or more non-aromatic monomers interpolymerizable therebetween. Such additional interpolymerizable monomers include, for example, C4-20 dienes, preferably butadiene or 5-ethylidene-2-norbornene. The olefinic polymers can also be characterized by their degree of branching of long or short chains and the distribution thereof. A class of olefinic polymers is generally produced by a high pressure polymerization process using a free radical initiator resulting in the traditional long chain branched low density polyethylene (LDPE). The LDPE used in the present composition usually has a density of less than 0.94 g / cc (ASTM D 792) and a melt index of 0.01 to 100, and preferably 0.1 to 50 grams per 10 minutes (determined by the Test Method). ASTM D 1238). Another class is that of linear olefin polymers which have an absence of long chain branches, as in traditional linear low density polyethylene (heterogeneous LLDPE) polymers or linear high density polyethylene (HDPE) polymers manufactured using Ziegler polymerization (e.g., U.S. Patent No. 4,076,698), sometimes called heterogeneous polymers. HDPE consists mainly of linear polyethylene chains. The HDPE employed in the present composition usually has a density of at least 0.94 grams per cubic centimeter (g / cc) as determined by ASTM Test Method D 1505, and a melt index (ASTM-1238) in the range of 0.01 to 100, and preferably 0.1 to 50 grams per 10 minutes. The LLDPE employed in the present composition generally has a density of 0.85 to 0.94 g / cc (ASTM D 792), and a melt index (ASTM-1238, condition 1) in the range of 0.01 to 100, and preferably 0.1 to 50 grams per 10 minutes. Preferably the LLDPE is an interpolymer of ethylene and one or more other α-olefins having from 3 to 18 carbon atoms, more preferably from 3 to 8 carbon atoms. Preferred co-monomers include 1-butene, 4-methyl-1-pentene, 1 -hexene and 1-octene. Another class is that of uniformly branched or homogeneous polymers (homogeneous LLDPE). The homogeneous polymers do not contain long chain branches and only have branches derived from the monomers (if they have more than two carbon atoms). Homogeneous polymers include those made as described in US Pat. No. 3,645,992 (Elston), and those made using single-site catalysts in a reactor having relatively high olefin concentrations, as described in US Pat. 5,026,798 and 5,055,438 (Canich). The uniformly branched / homogeneous polymers are those polymers in which the co-monomer is randomly distributed within a given interpolymer molecule and wherein the interpolymer molecules have a similar ethylene / co-monomer ratio within that interpolymer. The homogeneous LLDPE employed in the present composition generally has a density of 0.85 to 0.94 g / cc (ASTM D 792), and a melt index (ASTM-1238, condition 1) in the range of 0.01 to 100, and more preferably of 0. 1 to 50 grams per 10 minutes. Preferably the LLDPE is an interpolymer of ethylene and one or more other α-olefins having from 3 to 18 carbon atoms, more preferably from 3 to 8 carbon atoms. Preferred co-monomers include 1-butene, 4-methyl-1-pentene, 1 -hexene and 1-ketene. In addition there is the class of substantially linear olefin polymers (SLOP) which can be advantageously used in the component (B) of the mixtures of the present invention. These polymers have a processability similar to LDPE, but the strength and resistance of LLDPE. Similar to traditional homogeneous polymers, the substantially linear ethylene / α-olefin interpolymers have only a single melting peak, as opposed to heterogeneous ethylene / α-olefin interpolymers polymerized according to traditional Ziegler having two or more melting peaks ( determined using differential scanning calorimetry). Linear olefin polymers are substantially described in U.S. Patent Nos. 5,380,810; 5,272,236 and 5,278,272. The SLOP density measured in accordance with ASTM D-792 is generally from 0.85 g / cc to 0.97 g / cc, preferably from 0.85 g / cc to 0.955 g / cc, and especially from 0.85 g / cc to 0.92 g / cc . The melt index, in accordance with ASTM D-1238, Condition 190 ° C / 2.16 kg (also known as I2), of SLOPs is generally from 0.01 g / 10 minutes to 1000 g / 10 minutes, preferably from 0.01 g / 10 minutes to 100 g / l Ominutes, and especially from 0.01 g / 10 minutes to 10 g / l Ominutes. Also included are the ultra low molecular weight ethylene polymers and ethylene / α-olefin interpolymers described in WO Patent Application No. 97/01181 entitled Ultra Low Molecular Weight Polymers, filed January 22, 1997. These interpolymers of ethylene / α-olefin have melt indexes I2 greater than 1,000, or an average molecular weight number (Mn) of less than 1 1,000.

The most preferred homopolymers or interpolymers of aliphatic α-olefins having 2 to 20 carbon atoms and optionally containing polar groups are ethylene homopolymers; polypropylene homopolymers, co-polymers of ethylene and at least one other α-olefin containing from 4 to 8 carbon atoms; copolymers of propylene and at least one other α-olefin containing from 4 to 8 carbon atoms; copolymers of ethylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; copolymers of propylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; and terpolymers of ethylene, propylene and a diene. Especially preferred are polypropylene (PP), SLOP, heterogeneous and homogeneous LLDPE, LDPE, HDPE, especially isotactic polypropylene and rubber-hardened polypropylenes, or ethylene-propylene (EP) interpolymers, or ethylene-vinyl acetate co-polymers, or ethylene copolymers Acrylic acid, or any combination thereof. The charged polymer composition of the present invention may contain one or more additives, for example, antioxidants, such as phenols or clogged phosphites; light stabilizers, such as blocked amines; plasticizers, such as dioctylphthalate or epoxidized soybean oil; tackifiers, such as known hydrocarbon tackifiers; waxes, such as polyethylene waxes; process aids, such as oils, stearic acid or a metal salt thereof; interlacing agents, such as peroxides or silanes; dyes or pigments to the extent that they do not interfere with the desired physical properties of the charged polymer composition of the present invention. The additives are employed in equivalent amounts functionally known to those skilled in the art, generally in amounts of up to 30, preferably from 0.01 to 5, more preferably from 0.02 to 1 weight percent based on the total weight of the charged polymer composition. .

The charged polymeric compositions can be prepared by any convenient method, such as by dry blending interpolymer (s), the filler (s) and optional additives and mixing by subsequent melting, either directly into the extruder used to make the finished article, or by pre-melting in a separate extruder (for example, a Bambury mixer). The dry mixtures of the compositions can also be direct injection molded without pre-melt mixing. The blends can be processed into articles made by any suitable means known in the art. For example, the charged polymer composition can be processed in films or sheets or in one or more sheets of a multi-layer structure by known processes, such as calendering, blowing, molding or co-extrusion processes. Injection, compression, extrusion or blow molded parts can also be prepared from the charged polymer compositions of the present invention. Alternatively, the charged polymer compositions can be processed into foams or fibers. Useful temperatures for processing the interpolymer (s) in combination with the optional filler (s) and additives are generally 100 ° C to 300 ° C, preferably 120 ° C to 250 ° C, more preferably 140 ° C to 200 ° C. The manufactured articles of the present invention can be foamed. The foam layer can be produced by an extrusion process or from expandable or foamable particles, moldable foam particles or beads from which a sheet is formed by expansion and / or by coalescing and welding those particles. The foam structure can be made by a conventional extrusion process. The structure is generally prepared by heating a polymeric material to form a plasticized or melted polymeric material, incorporating therein a known foaming agent to form a foamable gel., and extrude the gel through a die to form the foam product. Prior to mixing with the foaming agent, the polymeric material is heated to a temperature at or above its glass transition temperature or melting point. The foaming agent can be incorporated or mixed with the molten polymeric material by means known in the art such as with an extruder, or a mixer. The foaming agent is mixed with the molten polymeric material at a high enough pressure to prevent substantial expansion of the molten polymeric material and to generally disperse the foaming agent homogeneously therein. Optionally, a core former in the melted or dried polymer mixture can be mixed with the polymer material before plasticizing or melting. The foaming gel is typically cooled to a lower temperature to optimize the physical characteristics of the foam structure. The gel is then extruded or transported through a die of desired shape to a zone of reduced pressure or less to form the foam structure. The die may have a substantially rectangular hole to produce a sheet of a desired width and height. Alternatively, the die may have multiple orifices to produce polymer threads that can be cut into beads. The zone of lower pressure is at a lower pressure than that in which the foamable gel is maintained before extruding it through the die. The lower pressure may be superatmospheric or subatmospheric (vacuum), but is preferably at an atmospheric level. The foam structure can also be formed into foam beads suitable for being molded into articles. To make the foam beads, discrete resin particles such as beads of granulated resin are suspended in a liquid medium in which they are substantially insoluble such as water; impregnated with a foaming agent by introducing the foaming agent into the liquid medium at a high pressure and temperature in an autoclave or other pressure vessel; and rapidly discharged to the atmosphere or a region of reduced pressure to expand to the shape of foam beads. This process is well taught in U.S. Patent Nos. 4,379,859 and 4,464,484. The foam beads can then be molded by any means known in the art, such as loading the foam beads into the mold, compressing the mold to compress the beads and heating the beads as with steam to effect coalescence and welding of the beads. pearls to form the article. Optionally, the beads can be impregnated with air or other foaming agent at a high pressure and temperature before being loaded into the mold. In addition, pearls can be heated before loading. The foam beads can then be cast into sheets by a suitable molding method known in the art. Some of the methods are taught in U.S. Patent Nos. 3,504,068 and 3,953,558. Various additives may be incorporated in the foam structure, such as stability control agents, core forming agents, pigments, antioxidants, acid scavengers, ultraviolet absorbers, flame retardants, process aids or extrusion aids. Some of the additives are described in more detail later. The manufactured articles of the present invention which are made from charged polymeric compositions comprising one or more thermoplastic interpolymers and one or more inorganic fillers in the aforementioned weight ratios have substantially improved hardness and tension moduli while generally maintaining good properties of elongation, such as elongation to breakage, stress to breakage and energy to breakage, compared to manufactured articles made from one or more corresponding thermoplastic interpolymers without the inclusion of a filler. In addition, articles made of the present invention generally have good thermal resistance and, depending on the type of load, improved ignition resistance. The charged polymeric compositions of the present invention can easily be extruded onto a substrate. Alternatively, the charged polymer compositions of the present invention can be extruded, milled or calendered as unsupported films or sheets, for example, to produce floor tiles, wall tiles, floor sheets or roof covers. They are particularly useful as layers, films, sheets or sound insulating boards or energy absorbers. Films, sheets or boards of a wide range of thicknesses can be produced. Depending on the intended end use, the useful thicknesses are generally from 0.5 to 20 mm, preferably from 1 to 10 mm. Alternatively, injection molded parts or blow molded articles, such as toys, containers, finishing and construction materials, automotive components, and other durable articles can be produced from the charged polymeric compositions of the present invention. The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be construed as such. The amounts are in parts by weight or percentages by weight unless otherwise indicated. TEST The properties of the polymers and mixtures are determined by the following test procedures. FusiónfMD index is determined by ASTM D-1238 (1979), Condition E (190 ° C, 2.16 kg). Stress stress, secant modulus, and elongation properties are measured using ASTM D-638, Type C. Elongation at break, breaking strength and breaking energy are measured at a tension rate of 5 min "1. The module The hardness is measured using a Hardness Tester for Shore A and D according to DIN 53505. Drum abrasion is measured according to ASTM F-510. The scratch test is measured using ASTM D 790-95A. It is carried out using a Universal Erichson Scratch Tester equipped with a 90-degree needle at 180 μm, a load of 0. 1 to 1.0 N is applied to this needle, and the width of the resulting line is measured after 30 days by means of a Perthen Surface Profiler. Width and depth of the line are expressed in micrometers. For indentation test, ASTM F 142-93 (Standard Test Method for Floor-McBurney Resilient Test Indentation) and a modified test are used. In the modified test, a load of 64 kg is applied via a cylindrical foot of 4.5 mm in diameter. The load is applied for 10 minutes and the initial indentation is measured. The residual indentation is measured after 60 minutes. For the modified test the indentations are reported as a percentage of the initial plate thickness. For residual indentation, the sample is given a range of "failure" if the notched cylindrical foot cuts and permanently damages the surface. The thermal transition temperatures are measured with differential scanning calorimetry (DSC) and dynamic mechanical spectroscopy (DMS). Preparation of Ethylene / Styrene Interpolymers, ESI-1, ESI-2, ESI-4. ESI-8, ESI-9 and ESI-10.

Reactor Description The single reactor used is a Continuous Stirred Tank Autoclave (CSTR) reactor, with 22.7 L oil jacket. Agitation is provided by a magnetically coupled stirrer with Lightning A-320 impellers. The reactor works full of liquid at 3,275 kPa. The process flow is in the background and outside the top. A heat transfer oil is circulated through the reactor jacket to remove some of the heat of reaction. After the outlet of the reactor there is arranged a flow meter micromoción that measures the flow and the density of solution. All lines at the reactor outlet are indicated with steam of 344.7 kPa and isolated. Procedure Ethylbenzene solvent is supplied to the mini-plant at 207 kPa. The feed to the reactor is measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controls the feed rate. At the discharge of the solvent pump a side stream is taken to provide large flow rates for the catalyst injection line (0.45 kg / hr) and the reactor agitator (0.34 kg / hr). These flows are measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves. Styrene monomer is supplied without inhibiting the mini-plant at 207 kPa. The feed to the reactor is measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controls the feed rate. The styrene stream is mixed with the remaining solvent stream. The ethylene is supplied to the mini-plant at 4, 137 kPa. The ethylene stream is measured by a Micro-Motion mass flow meter just before the Research valve that controls the flow. Brooks flow meters / controllers are used to deliver hydrogen to the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture is combined with the solvent / styrene stream at room temperature. The temperature of the solvent / monomer as it enters the reactor is reduced to about 5 ° C by a glycol-5 ° C exchanger in the jacket. This current enters through the bottom of the reactor. The three component catalyst system and its solvent wash also enters the reactor through the bottom, but through a hole different from that of the monomer stream. The composition of the three component catalyst system is as follows: component molar ratio molar ratio catalyst catalyst catalyst co-catalyst catalyst titanium olimero boron aluminum boron / Ti Al / Ti ESI- 1 type 1 MMAO-3A type 1 3: 1 8: 1 ESI-2 type 1 MMAO-3A type 1 2: 1 5: 1 ESI-4 type 1 MMAO-3A type 3 2: 1 5: 1 ESI-8 type 1 MMAO-3A type 2 1 .25: 1 12: 1 ESI-9 type 2 MMAO-3A type 2 1 .25: 1 10: 1 ESI- 10 type 2 MMAO-3A type 2 1.25: 1 10.1 The titanium catalyst type 1 is (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene. The titanium catalyst type 2 is (t-butylamido) dimethyl (3-phenyl-s-indacen-1-yl) silanetitanium (IV) dimethyl. The aluminum catalyst component is a commercially available modified type 3A (MMAO-3A) meta-lumoxane available. The boron co-catalyst type 1 is tris (pentafluoro phenyl) borane. The boron type 2 catalyst is bis-hydrogenated tallowalkyl methylammonium tetrakis (pentafluorophenyl) borate. The boron co-catalyst type 3 is a mixture of methyl (Ci8-22-alkyl) ammonium tetrakis (pentafluorophenyl) borates and methyl di (Ci8-22-alkyl) ammonium tetrakis (pentafluoro phenyl) borates. The preparation of the catalyst components took place in an inert atmosphere glove compartment. The diluted components are padded and loaded with nitrogen cylinders in the runner tanks of the catalyst in the process area. From these run-off tanks the catalyst It is pressurized with piston pumps and the flow is measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst wash solvent just before entering through a single injection line into the reactor. The polymerization is stopped with the addition of a catalyst nullifier (water mixed with solvent) in the product line of the reactor after measuring the density of the solution with the micromotion flow meter. Other polymeric additives can be added with the catalyst nullifier. A static mixer in the line provides dispersion of catalyst nullifier and additives in the effluent stream of the reactor. This current then enters post-reactor heaters that provide additional energy for the solvent removal flash. This flashing occurs as the effluent from the post-reactor heater exits and the pressure drops to 3, 275 kPa to approximately 250 mm absolute pressure in the reactor pressure control valve. This flashed polymer enters a hot oil jacket devolatilizer. Approximately 85 percent of the volatiles are removed from the polymer in the devolatilizer. The volatiles exit through the top of the devolatilizer. The stream is condensed with a jacketed glycol exchanger, enters the suction of a vacuum pump and is discharged to a solvent separation tank of glycol jacket and styrene / ethylene.

Solvent and styrene are removed from the bottom of the container and ethylene from the top. The ethylene current is measured with a Miro-Motion mass flow meter and its composition is analyzed. The ethylene vent measurement plus a calculation of the gases dissolved in the solvent / styrene stream are used to calculate the ethylene conversion. The polymer separated in the devolatilizer is pumped out with a rotary gear pump to a ZSK-30 devolatilizing vacuum extruder. The dried polymer leaves the extruder as a single cord. This cord or thread is cooled as it is pulled through a water bath. Excess water is removed from the cord by blowing air and the cord is cut into balls with a cord cutter. The amounts of monomer and polymerization conditions are given in Table IA. The properties of the polymer are given in Table IC below. Table IA cc / min., standardized at 1 atm (760 torr) and ° C.

Preparation of Ethylene / Styrene Interpolymers ESI-3, ESI-5, ESI-6 and ESI-7 The Polymer is prepared in a stirred, semi-continuous loading reactor of 1514 liters. The reaction mixture consists of approximately 946 liters of styrene and a solvent comprising a mixture of cyclohexane (85% by weight) and isopentane (15% by weight). Before the addition, the solvent, styrene and ethylene are purified to remove water and oxygen. The inhibitor in styrene is also eliminated. The inerts are removed by purging the container with ethylene. The container is then pressurized to a fixed point with ethylene. Hydrogen is added to control the molecular weight. The temperature in the container is controlled at a fixed point by varying the water temperature of the jacket in the container. Prior to polymerization, the vessel is heated to the desired working temperature and the catalyst components, ie catalyst (tert-butylamido) dimethyl (tetramethyl-? 5-cyclopentadienyl) silane dimethyl tithium (IV), CAS # 135072-62- 7, Tris (pentafluorophenyl) boron, CAS # 001 109-15-5, methyl-aluminoxanotype 3 A modified, CAS # 146905-79-5, are controlled in flow, on a ratio basis per mole of l: / 3: 5 respectively, combined and added to the container. After starting, the polymerization is allowed to proceed with ethylene supplied to the reactor as necessary to maintain the container pressure. In some cases, hydrogen is added to the headspace of the reactor to maintain a molar ratio to the ethylene concentration. At the end of the run, the flow of the catalyst is stopped, the ethylene is removed from the reactor, then approximately 1000 ppm of Irganox ™ 1010 is added to the solution and the polymer is separated from the solution. The resulting polymers are separated from the solution either by stripping with steam in a vessel (in the case of ESI-5). In the case of steam-stripped material, an additional process is required in equipment such as the extruder to reduce residual moisture and any unreacted styrene. The amounts of monomer and polymerization conditions are given in Table IB. The properties of the polymer are given in Table IC. Table IB IC table na = not analyzed Table II: Other Materials Used in the Examples Abbreviated Product Name Ind. Fusion Density (gm / 10 min) (gm / cc) ITP-1 AFFINITY ™ DSH 8501.00 POP 1.0 0.871 (ethylene-1-octene copolymer) ITP-2 AFFINITY ™ DSH 1500.00 1.0 0.902 (ethylene-1-ketene copolymer) ITP-3 AFFINITY ™ SM 8400 30.0 0.871 (ethylene-1-ketene copolymer) ITP-4 AFFINITY ™ SM 1300 30.0 0.902 (ethylene-1-ketene copolymer) MAH Dow XU-60769.04 2.5 0.955 (polyethylene grafted with maleic anhydride, 1.0% maleic acid) CaC03 for examples 1-25, 62 and 63 obtained from Pfizer ATF-40 (limestone, 40 mesh) CaCO, for examples 26-48: Whingdale White (average particle size: 6 microns) CaCO, for examples 49-51, 53 and 54 obtained from Omya BSH (average particle size: 2.4 microns) alumina trihydrate: Martinal OL 104C (Registered Trademark) silica commercially available as Laevisil SP (Registered Trademark) Silitin N85 (MR): a 50/50 mixture of dolomite and silica.

Talcum Owen Corning OC 187A-AA SHELLFLEX ™ 371 Oil Examples 1 to 25 The plates of Examples 1 to 25 were prepared via the following steps: 1) mixed in Haake pot, 2) milled in rollers, and 3) compression molded into plates. A Haake mixer equipped with a 3000 Rheomix pot was used. All the components of the mixture were added to the mixer, and the rotor was operated at 190 ° C and 40 rpm for 10 to 15 min. The material was then drained off the Haake, and fed to a Farrel two-roll mill of 15.24 cm in diameter by 30.48 cm in width programmed at a surface temperature of 175 ° C. The sheet was either removed after rolling 180 degrees or allowed to roll 540 degrees before releasing it. The sheet was then cut and compression molded into plates 3,175 mm thick by 101.6 mm by 101.6 mm with a Pasadena Hydraulics Incorporated (PHI) press. The press was operated at 205 ° C in a minimum pressure preheating mode for 3 minutes, and then it was operated up to 15 tons for two minutes. The plates were then removed from the heat and cooled to 15 tons for 3 minutes. The properties of the compression molded plates were measured as indicated above. Tables III and IV list the compositions and physical properties resulting from Examples 1 to 23 according to the present invention and Comparative Examples 24 and 25 for 60% loaded and 84% loaded formulations, respectively.

Table III nt = not tested Examples 1 to 8 illustrate that coupling polymeric additives or agents were not required to achieve good solid state and charge retention properties. The products of Examples 1 to 10 were useful as homogenous sheets with charge, such as floor coverings, or as a single layer in a heterogeneous structure. The products of Examples 1 to 10 are especially suitable for floor laminates.

Table IV Table IV continued * Comparative Example np = not tested The plates of examples 1 to 23 have a considerably higher scratch resistance than the plates of comparative examples 24 and 25. Examples 1 to 21 illustrate that no polymeric coupling additives or agents were required to achieve good properties of solid state and charge retention. The plate of Example 13 showed an exceptional combination of resistance to flexibility and indentation, and was particularly useful in or as a floor tile product with good installation ability and good conformability to uneven and contoured surfaces. The products of Examples 1 to 23 were useful as homogeneous sheets with fillers, such as floor covering, or as a single layer in a heterogeneous structure. The products of examples 1 to 23 were especially suitable for floor tile products. Examples 26 to 48 In Examples 26 to 48 the plates were produced as described above in Examples 1 to 27 except that a roll milling process was not applied and the dimensions of the plates were 127 mm by 127 mm by 2.03 mm.

Table V Examples 49 to 63 The plates are prepared by 1) mixing, 2) roller milling, 3) pressing in the form of plates. In the mixing step the polymers were melted and the desired amount of filler was added in small portions. The mixing time was 10 to 15 minutes. In the step of milling in rollers the following conditions were applied: The sheet produced by the roller mill was then cut and loaded into a mold consisting of a steel plate covered with a fluorocarbon tetrafluoroethylene polymer material (TEFLON ™) and a 28 cm by 28 cm by 0.2 cm frame. The mass of the sheet cut within the frame was the volume of the mold, i.e. 156.8 cm3, by density of the composition + 10%. The mold was closed with a steel plate and pressed at an elevated temperature. The material was pre-pressed for 5 minutes at 8 bar and for 3 minutes at 200 bar machine pressure at a temperature of 175 ° C (Examples 49-60) at 160 ° C (Examples 62 and 63). The mold was placed between a steel bottom plate cooled by water and upper plate and cooled to room temperature for 5 minutes. Sheets of 2 mm thickness were produced.

• Comparative Example (not previous art) Examples 49 to 63 illustrate that coupling polymeric additives or agents were not required to achieve good solid state and charge holding properties. The comparison between Comparative Example 52 and Examples 53-60 illustrates the high elongation to the final tension of polymeric compositions with fillers of the present invention.

Claims (17)

1. CLAIMS 1. A polymer composition with fillers comprising: (A) from 5 to 90 percent of one or more substantially random thermoplastic interpolymers prepared by the polymerization of one or more α-olefin monomers with one or more aromatic vinylidene monomers and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally with other ethylenically unsaturated polymerizable monomer (s), the aliphatic vinylidene monomer (s) or Clogged cycloaliphatic (s) that correspond to the formula: A1 R1 - C = C (R) 2 wherein A1 is an aliphatic or cycloaliphatic, sterically bulky, substituent of up to 20 carbons excluding α-olefin monomers contag from 2 to 20 carbon atoms and having a linear aliphatic structure, R 1 is hydrogen or an alkyl radical contag 1 to 4 carbon atoms; each R2 is independently hydrogen or an alkyl radical contag from 1 to 4 carbon atoms, or alternatively R1 and A1 together form a ring system, and (B) from 10 to 95 percent of one or more inorganic fillers, being based on the amounts of (A) and (B) in the total weight of (A) and (B). The polymeric composition with fillers of claim 1 wherein said one or more interpolymers contain interpolymerized: from 35 to 99.5 mole percent of one or more α-olefin monomers; and from 0.5 to 65 mole percent of one or more aromatic vinylidene monomers and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged; and optionally other polymerizable ethylenically unsaturated monomer (s). 3. The polymeric composition with fillers of claim 1 or claim 2 wherein said interpolymer is an interpolymer of ethylene and styrene. The polymeric composition with fillers of any one of claims 1 to 3 comprising from 40 to 90 percent of one or more inorganic fillers, based on the total weight of the interpolymer (s) and the (s) load (s). 5. The polymeric composition with fillers of any one of claims 1 to 4 comprising one or more inorganic ionic fillers. 6. The polymeric composition with fillers of claim 5 wherein the filler is talc, calcium carbonate, barium sulfate, alumina trihydrate, magnesium hydroxide, glass fiber or a mixture thereof. The polymeric composition with fillers of any one of claims 1 to 6 wherein the total amount of the interpolymer (s) (A) and the inorganic filler (s) (B) is at least 50 percent, based on the total weight of the polymer composition with fillers. The polymeric composition with fillers of any one of claims 1 to 7 comprising up to 50 weight percent of one or more additional polymer component (s), based on the total weight of the composition polymer with loads. 9. The polymeric composition with fillers of any one of claims 1 to 8 further comprising a coupling agent. 10. The polymer composition with fillers of any one of claims 1 to 9 further comprising an obstructed amine. 11. The polymeric composition with fillers of any one of claims 1 to 10 further comprising stearic acid or a metal salt thereof. 12. A manufactured article made from the polymer composition of any one of claims 1 to 11. 13. The manufactured article of claim 12 in the form of a film or sheet. 14. The manufactured article of claim 12 in the form of a cover for floor, wall or ceiling. 15. The manufactured article of claim 12 in the form of a foam or in the form of fibers. 16. The manufactured article of claim 12 made by injection molding, compression molding, extrusion blow molding. 17. A multilayer structure wherein at least one layer is made from the polymer composition of any one of claims 1 to 11.